Insect control with an hydrogenated naphthylamine



Patented Jan. 15, 1952 UNITED STATES PATENT OFFICE.

I'NsEo'r doi'vltrnol. WITH AN HYDRO: GENATED NAPHTHYLAMINE Robert D. Englert, Henry J. Gefiovich, and Michel Pijoar'r, Bender; 0010., assigncr'slto" The chem ical Foundatinmma, New York, N. Y., a corporation of York 1% ma'w'iiig'. KpplicationFebriiary 28'', 1941',

' serial No. 731,704 6 claims.- (01. 167-32) This invention mates to an improved method or controlling insects.

It has been previously show'nj in application, Serial No. 673,035, filed May 29 f19 l'6,- now" Patent No. 2,578,736, that certainnaphthalene derive) tives, especially those resulting from chloral condensations of naphthalene derivatives exhibit marked insecticidal action. In the course of investigation of the eflicacy of these compounds, as insecticides, it has been further ascertained that certain of the intermediate compounds, in themselves, present very marked insecticidal properties. It has been determined, for example, that hydrogenated naphthylamines such as 5,- amino, 12,3,4, tetrahydro napthalene, 2,amino, 1,2,3,4, tetrahydro naphthalene, and decahydro alpha napthylamine, which for the sake of a term can be designated amino substituted hydrogenated naphthylenes, present marked insecticidal action. We have also found that this type of insecticidal property is exhibited by the products obtained by a Schiff-base condensation reaction of hydrogenated naphthylamine and chloral, that isto say a reaction product in which the chloral group is linked directl with the amino, yielding l, trichloroethane tetrahydronaphthylamine.

The eificacy Of these types of compounds is evidenced by their action against such typical insects as flies and roaches as is indicated by the data in the table below. In the tests from which this data was derived the test insects were contacted with 0.01 ml. of a 10% solution of the indicated compound and the killing time was observed.

The residual eifectiveness of these compounds is from 50 to 80 hours. By this is meant that insects brought into contact with surfaces coated with a 10% solution of the compound, applied 50 to 80 hours previously, were killed.

The compounds 2 ,-a-miiio, 1,2,3,4, tetra naphthalene, 5,amino,- 1,2,3,4,- newsman-rape: thalene were prepared as follows:

1 21101 or either alpha or betdnaphthylamine was" dissolvedin absolute ethyl alcohol inthe pi once of 20 gms. of activated Raney nickel was then hydrogenated at 15c atmospheres of h-yd gen at a temperature of 150 C. until theoretical absorption of hydrogenoccurred. The bomb was then cooled, the alcohol was removed by distillation and the residue wasdistilled and two fractions collected. The first fraction, distilling between to C. at 20 mm. pressure consisted of incompletely hydrogenated decahydronaphthylamines derived primarily from the alpha naphthylamine. The second fraction, distilling between to 146 C. under 16 mm. pressure was collected and was found to consist of two compounds, namely, 2,amino, 1,2,3,4, tetrahydronaphthalene (refractive index 1.5750 at 27 C.) and 5,amino, 123,4, tetrahydronaphthalene (refractive index 1.5829 at 27 C.)

The substantially pure decahydronaphthylamine was obtained by the hydrogenation of alpha naphthylamine under the stated conditions:

The compound 1,trichloroethane tetrahydronaphthylamine was prepared as follows:

10 gms. of dehydrated chloral were dissolved in 50 ml. of petroleum ether and this was added to a solution of 10 gms. of beta, 1,2,3,4, tetrahydronaphthylamine in 50 ml. of anhydrous ethyl ether. The vigorous reaction was allowed to continue for approximately 30 minutes during which the ether was evaporated. The residue was distilled and the fraction distilling over at 192 to 196 C. under 12 mm. pressure was collected.

While in the previous application referred to it was shown that chloral condensation products of naphthalene or naphthol derivatives possessed insecticidal properties it, is now found that in the case of naphthylamine such chloral condensation is not necessary to impart this desired insecticidal property. As disclosed herein, it is possible, by the simple expedient of hydrogenating naphthylamines to obtain products with insecticidal properties substantially equal to those produced by chloral condensation. Thus, it is seen certain hydrogenated naphthylamines serve as excellent contact insecticides possessing marked lethal action.

While certain preferred insecticidal compounds have been described it is to be understood that these are given to illustrate the novel concept of utilizing hydrogenated naphthylamines as effective contact insecticides.

We claim:

1. An improved method of controlling insects which comprises contacting the insects with an insecticide composition comprising as an effective ingredient hydrogenated naphthylamine dissolved in kerosene.

2. An improved method of controlling insects which comprises contacting the insects with an insecticide comprising as an efiective ingredient 5,amino, 1,2,3,4 tetrahydronaphthalene dissolved in kerosene.

3. An improved method of controlling insects which comprises contacting the insects :with an insecticide comprising a 10% solution of 5,amino, 1,2,3,4, tetrahydronaphthalene in kerosene.

4. A method of controlling insects which comprises contacting the insects with an insecticide comprising a 10% solution of 2,amino, 1,2,3,4, tetrahydronaphthalene in kerosene.

5. A method of controlling insects which comprises contacting the insects with a 10% solution of 1,trich1oroethane tetrahydronaphthylamine in kerosene.

6. A method of controlling insects which comprises contacting the insects with an insecticide comprising as an efiective ingredient a 10% solution of a hydrogenated naphthylamine in kerosene.

ROBERT D. ENGLERT. HENRY J. GERJOVICH. MICHEL PIJOAN.

hole "Tetrahydronaphthylamine, alpha.

4 REFERENCES CITED The following references are of record in the (file of this patent:

FOREIGN PATENTS Number Country Date 506,928 Great Britain June 6, 1939 290,175 Great Britain Aug. 7, 1929 302,003 Germany Nov. 24, 1917 324,757 Germany Sept. 3, 1920 OTHER REFERENCES Hackhs Chem. Dict., 3rd. ed., 1944, p. 840, ar-

py in Div. 43.

Fink et al.: U. S. D. A. Bur. of Ent. & Plant Quar. Mimeo Pub. E-425 entitled, Toxicity Tests with Synthetic Organic Compounds Against Culcine Mosquito Larvae, March, 1938, pp. 1-4, 15. 167-22.

McAllister et al.: J. Econ. Ent., vol. 23 No. 6, Dec. 1930, pp. 907-913, 919. (Comp. No. 28.) (Copy in Div. 43.)

Allers et al.: Chem. Abst, vol. 24, p. 5862 (1930). (Copy in Pat. Ofl. Lib.) 

1. AN IMPROVED METHOD OF CONTROLLING INSECTS WHICH COMPRISES CONTACTING THE INSECTS WITH AN INSECTICIDE COMPOSITION COMPRISING AS AN EFFECTIVE INGREDIENT HYDROGENATED NAPHTHYLAMINE DISSOLVED IN KEROSENE. 